Chain-selective synthesis of fuel components and chemical feedstocks

ABSTRACT

A method comprising providing a starting composition comprising a polyunsaturated fatty acid, a polyunsaturated fatty ester, a carboxylate salt of a polyunsaturated fatty acid, a polyunsaturated triglyceride, or a mixture thereof; self-metathesizing the starting composition or cross-metathesizing the starting composition with at least one short-chain olefin in the presence of a metathesis catalyst to form self-/cross-metathesis products comprising: cyclohexadiene; at least one olefin; and one or more acid-, ester-, or salt-functionalized alkene; and reacting cyclohexadiene to produce at least one cycloalkane or cycloalkane derivatives. A method for producing cycloalkanes for jet fuel by providing a starting composition comprising at least one selected from the group consisting of algal and polyunsaturated vegetable oils, subjecting the starting composition to metathesis to produce metathesis product comprising at least one olefin, cyclohexadiene, and at least one acid-, ester-, or salt-functionalized alkene, and reacting the at least one olefin and cyclohexadiene to form cycloalkane(s).

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

This invention was made with U.S. government support under Contract No.W911NF-07-C-0046 awarded by the Defense Advanced Research ProjectsAgency (DARPA). The government has certain rights in this invention.

CROSS-REFERENCE TO RELATED APPLICATIONS

Not applicable.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates generally to the production of fuelblendstocks and chemical products. More specifically, the presentinvention relates to a process for the simultaneous production ofchemical feedstocks and fuel blendstocks such as jet fuel fromunsaturated and polyunsaturated vegetable oils and/or algal oils. Stillmore specifically, the present invention relates to a process for thesimultaneous production of chemical feedstocks and fuel blendstocks inthe absence of thermal or catalytic cracking of carbon chains intonumerous small fragments and/or without reduction of ester moieties.

2. Background of the Invention

The ability to exchange alkylidene units of unsaturated vegetable oilspresents unique opportunities for synthesis of desirable-chain-lengthcompositions. The exchange reaction employed is known as olefinmetathesis. Olefin metathesis can be catalyzed by a variety oftransition metal compounds that can form a carbene intermediate with thealkylidene fragment. A description of olefin metathesis may be found inthe text Olefin Metathesis by K. J. Ivin (Academic Press, New York,1983).

The cross-metathesis of unsaturated fatty esters with alpha-olefins hasbeen known for some time. As described by E. Verkuijlen et al. (Recl.Tray. Chim. Pays-Bas 1977, 96(8), M86-M90), co-metathesis of methyloleate and 3-hexene gives 3-dodecene and methyl 9-dodecenoate. Recentpatent applications address the use of the unsaturated ester portion ofthe metathesis products of vegetable oils. For example, in U.S. PatentApplication 2005/0154221 A1, Lysenko et al. disclose conversion of shortmonounsaturated ester product to an aldehyde ester and subsequently toamino esters or hydroxyl esters, which are useful polymer intermediates.In PCT Application PCT/US2007/021931, Abraham et al. disclose conversionof the unsaturated ester to an amino ester.

A disadvantage of conventional metathesis processes is that thefeedstock is generally converted into a product with limited usefulness.Accordingly, there is a need in the art for methods integratingcross-metathesis and/or self-metathesis with processing whereby cyclicdifunctional monomers useful for the synthesis of polyurethane,polyamide, and other valuable polymers can be produced, as well asdesired distributions of alkenes and unsaturated fatty esters that canbe converted to desired fuel components. In applications, the methodprovides for conversion of substantially all of a biomass feedstock tohigh-value fuel blendstock components and chemical intermediaries.

BRIEF SUMMARY

Herein disclosed is a method comprising: providing a startingcomposition comprising a polyunsaturated fatty acid, a polyunsaturatedfatty ester, a carboxylate salt of a polyunsaturated fatty acid, apolyunsaturated triglyceride, or a mixture thereof; self-metathesizingthe starting composition or cross-metathesizing the starting compositionwith at least one short-chain olefin in the presence of a metathesiscatalyst to form metathesis products comprising: cyclohexadiene; one ormore olefin compounds; and one or more acid-, ester-, orsalt-functionalized alkene comprising at least one carbon-carbon doublebond; and reacting at least a portion of the cyclohexadiene to produceat least one selected from the group consisting of cycloalkanes andcycloalkane derivatives. In embodiments, at least a portion of thecycloalkanes are used for fuel blendstock. In applications, reacting theat least a portion of the cyclohexadiene comprises catalyticallyreacting at least a portion of the cyclohexadiene to producedisubstituted or di-functionalized cyclohexane derivatives.

The disubstituted or di-functionalized cyclohexane derivatives may havethe formula C₆H₁₀X₂, where X is selected from the group consisting ofCN, CHO, and CH₂NH₂. In embodiments, the disubstituted ordi-functionalized cyclohexane derivatives arecyclohexanedicarboxaldehyde derivatives having the formula C₆H₁₀(CHO)₂.The method may further comprise reducing the carboxaldehyde groups toform alcohol groups.

In applications, the disubstituted or di-functionalized cyclohexanederivatives are dinitrile derivatives having the formula C₆H₁₀(CN)₂. Themethod may further comprise hydrolyzing the nitrile groups to formcarboxylic acid groups. The method may further comprise hydrogenatingthe nitrile groups to form amine groups.

In applications, the cycloalkane derivatives comprise alkylcyclohexanederivatives having the formula C₆H₁₁R, where R is selected from alkylgroups. Reacting the at least a portion of the cyclohexadiene maycomprise reacting cyclohexadiene with a feed comprising olefins. Inembodiments, at least a portion of the olefins in the feed comprisingolefins were produced via the metathesis reaction.

In applications, the method further comprises converting at least one ofthe metathesis products to produce at least one fuel blendstockcomponent selected from alkanes, isoalkanes, and cycloalkanes. Inapplications, the at least one fuel blendstock has a chain length in therange of from eight to fourteen carbon atoms. The fuel blendstock may besuitable for use in at least one selected from the group consisting ofJP-4, JP-5, JP-8, Jet A, and Jet A1 fuels. In applications, the fuelblendstock is tailored by limiting the metathesis reaction by adjustingat least one selected from the reaction temperature, reaction time,amount of catalyst, and amount of co-reactant olefin, whereby a desiredcomprehensive distribution of chain lengths is obtained from partialcompletion of the metathesis reaction.

In embodiments, the method further comprises converting at least aportion of the metathesis products to azeleic acid. The startingcomposition may comprise vegetable oil. The starting composition maycomprise algal oil.

In embodiments, the one or more olefin metathesis product compriseslight olefins selected from 1-propene and 1-butene, and the methodfurther comprises oligomerizing the light olefin product to producekerosene fuel components having chain lengths in the range of from abouteight to sixteen carbons. In applications, oligomerizing comprisestreatment with strong acid.

In applications, the method comprises cross-metathesis of a startingcomposition comprising algal oil, and the at least one short chainolefin comprises ethylene. In embodiments, the at least one short chainolefin consists essentially of ethylene. In applications, the methodcomprises cross-metathesis of a starting composition comprisingomega-unsaturated vegetable oil containing linolenic acid. The vegetableoil may be selected from the group consisting of flaxseed, rapeseed,camelina, soy, and palm oils.

In applications, the starting composition comprises algal oil, and themetathesis product comprises one or more olefin compound determined bythe selection of the at least one short chain olefin co-reactant, anunsaturated carboxylic acid or ester with five or more carbons andunsaturation at C-4, and a saturated ester fraction. The method mayfurther comprise processing the saturated ester fraction via selectivelipase reaction. In embodiments, selective lipase reaction compriseslipase-catalyzed interesterification of an acyl portion of the saturatedester fraction with canola oil, and interesterification produces alow-melting point modified triglyceride comprising saturated andmonounsaturated fatty acids and having a melting point in the range offrom about 90° F. to about 100° F. In applications, the method furthercomprises producing a heat-absorbing material from the low-melting pointmodified triglyceride. The heat-absorbing material may comprise a panelthat is capable of absorbing external or internal heat, when in closecontact with human skin, maintaining the skin at normal skintemperature.

Also disclosed herein is a method of producing at least one fuel or fuelcomponent and at least one chemical product from a starting compositioncomprising a polyunsaturated fatty acid, a polyunsaturated fatty ester,a carboxylate salt of a polyunsaturated fatty acid, a polyunsaturatedtriglyceride, or a mixture thereof, the method comprising:self-metathesizing the starting composition or cross-metathesizing thestarting composition with at least one short-chain olefin in thepresence of a metathesis catalyst to form metathesis productscomprising: cyclohexadiene; one or more olefin compounds; and one ormore acid-, ester-, or salt-functionalized alkene comprising at leastone carbon-carbon double bond; utilizing a first portion of themetathesis products to produce a fuel blendstock; and utilizing a secondportion of the metathesis products to produce a chemical product. Inembodiments, the chemical product is selected from difunctionalcyclohexane derivatives and disaturated acyl mono-oleyl glycerideshaving melting points of less than 100° F.

Thus, embodiments described herein comprise a combination of featuresand advantages intended to address various shortcomings associated withcertain prior processes. The various characteristics described above, aswell as other features, will be readily apparent to those skilled in theart upon reading the following detailed description and by referring tothe accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

For a detailed description of the preferred embodiments of theinvention, reference will now be made to the accompanying drawings inwhich:

FIG. 1 is a flow diagram of an integrated fuel production and chemicalproduction process according to this disclosure.

FIG. 2 is a schematic of an integrated fuel and chemical productionprocess comprising cross-metathesis of oleate esters with alpha-olefinsand subsequent downstream processing.

FIG. 3 is a schematic of an integrated fuel and chemical productionprocess, according to an embodiment of the invention, comprisingcross-metathesis of vegetable oil (linoleyl part of triglyceride) ormethyl ester (linoleate methyl ester) and downstream processing.

FIG. 4 is a schematic of a downstream processing method, according to anembodiment of the invention, for synthesizing cycloparaffins andalkylaromatics via acid-catalyzed reaction of cyclohexadiene withalpha-olefins.

FIG. 5 is a schematic of a downstream processing method, according to anembodiment of the invention, for synthesizing disubstituted cyclohexaneintermediates suitable for synthesis of polymers.

FIG. 6 is a schematic of an integrated fuel and chemical productionprocess, according to an embodiment of the invention, comprisingcomplete metathesis of algal oil and downstream processing, whereincomplete metathesis comprises substantially complete reaction of thepolyunsaturated chains of the algal oil.

FIG. 7 is a schematic of an integrated fuel and chemical productionprocess, according to an embodiment of the invention, comprising partialmetathesis of algal and/or vegetable fatty acid methyl ester(s) or“FAME,” and downstream processing of metathesis products; partialmetathesis comprises limited (partial) reaction of the polyunsaturatedchains of the algal FAME and/or vegetable FAME to provide distributionsof chain lengths in the resulting products.

In the figures, like numerals are used to refer to like steps, forexample, 100-series numerals (e.g., 100, 101, 102, etc.) refer tometathesis steps, 200-series numerals (e.g., 200, 201, 202, etc.) referto downstream processing steps, 300-series numerals (e.g., 300, 301,302, etc.) refer to separation steps, 400-series numerals (e.g., 300,301, 302, etc.) refer to fuel production downstream processing steps,500-series numerals (e.g., 400, 401, 402, etc.) refer to chemicalproduction downstream processing steps, and so on. In instances, a steplabeled with a fuel processing or 400-series numeral may be suitable asa chemical production or 500-series step as well, and vice versa.

Notation and Nomenclature

The term “spec fuel” as used herein refers to fuel described by nationalor international standards wherein the density, boiling range, freezingpoint, flash point, aromatic content, and/or other specifications aresatisfied by testing procedures.

The term “R group” as used herein refers to methyl or triglycerylgroups. The term “R′ group” refers to hydrogen, or alkyl groups havingfrom 1 to 12 carbons; desirably, R′ groups are selected from hydrogen,methyl, ethyl, and propyl groups. Similarly, “R″ groups” refer to alkylgroups having from 1 to 12 carbon atoms, or hydrogen.

DETAILED DESCRIPTION

Overview. Herein disclosed is a process whereby a mixture of valuablechemical intermediates is produced along with fuel product(s) that canbe tailored to meet desired fuel specifications. For example, the fuelproduct may be tailored to meet jet fuel specification JP-8.

The present invention describes methods for the integration ofmetathesis (cross-metathesis and/or self-metathesis) reaction(s) withprocessing for formation of alkenes, cyclohexadiene, and unsaturatedfatty esters, acids, or salt-functionalized alkenes that can be used toproduce fuel components and can also be used to produce desirablechemical feedstocks. For example, the disclosed process can be used toproduce cyclic difunctional monomers useful for synthesis ofpolyurethane, polyamide, and other valuable polymers, and/or a desireddistribution of alkenes and unsaturated fatty esters, that can beconverted to desirable distributions of specific fuel components. Thefuel components can be used to prepare, for example, diesel fuelblendstocks and/or jet fuel. The disclosed integration of metathesis andsubsequent downstream processing of metathesis products may providesubstantially complete (i.e. approaching one hundred percent) use of astarting composition (also referred to as a feedstock).

FIG. 1 is a flow diagram of an integrated fuel production and chemicalproduction process 10 for the production of chemical feedstocks and fuelblendstocks according to this disclosure. Process 10 comprisesmetathesis at block 100 and downstream processing at block 200. At block100, metathesis is used to convert a starting composition intometathesis product comprising cyclohexadiene; one or more olefincompounds; and one or more acid-, ester-, or salt-functionalized alkenecomprising at least one carbon-carbon double bond. At block 200,metathesis products are processed to provide at least one chemicalfeedstock, at least one fuel blendstock component, or, desirably, both.As indicated in the flow diagram of FIG. 1, downstream processing atblock 200 comprises separation of metathesis products 300, production offuel blendstock at block 400 from a first portion of the separatedmetathesis products, and production of chemical feedstock at block 500from a second portion of the separated metathesis products.

In embodiments, the present invention is directed to a process for theproduction, from unsaturated and/or polyunsaturated oils (e.g.,vegetable oils), of both fuel blendstocks (including, withoutlimitation, biodiesel fuel, and/or jet fuel), and polymer intermediates(i.e. components utilized to produce polymers) without necessitatingcracking into smaller fragments and/or without reduction of the estermoiety.

The key to successfully processing a starting composition, e.g. atriglyceride vegetable oil containing mainly C18 fatty esters, and/orother triglycerides, such as crambe oil or algal oils containing C14 toC22 fatty esters, to fuels and chemicals with desirable combustion andphysical properties is to generate the appropriate range of moleculesizes in a target molecular composition. The fuel and chemicalproduction method of this disclosure provides for production of suchfuels and chemicals by reformation of C14 to C22 chains according to theplacement of the unsaturated bonds in the fatty acid chains of thestarting composition.

In the present invention, metathesis reactions are integrated with otherprocesses such that suitable-chain-length fuel components and chemicalsare produced. Metathesis at stage 100 causes interchange of pairs ofchain units between fatty acid esters of vegetable and/or algal oils orbetween oil components and suitable olefins. The metathesis products ofmetathesis stage 100 are processed in the second stage, downstreamprocessing 200, to provide a variety of fuel and chemical products.Downstream processing steps include, without limitation, one or more ofseparation of metathesis products, hydrogenation of unsaturatedproducts, recombination of selected initial metathesis products viaalkylation reactions, isomerization reactions, and additional separationsteps.

The types of oils and acids suitable for use in a starting compositiontreated by the disclosed method contain unsaturated and polyunsaturatedfatty acids that exist in various proportions along with saturated fattyacids in vegetable oils. Examples of such useful oils and acids, and adescription of the major constituents thereof, are presented in Table 1below.

TABLE 1 Oils and Acids Suitable for Use in Starting CompositionComponent Description of Major Constituent(s) Oleic Acid C18monounsaturated fatty acid (C18:1) Δ9 Linoleic Acid C18 diunsaturatedfatty acid (C18:2) Δ9, 12 Linolenic Acid C18 triunsaturated fatty acid(C18:3) Δ9, 12, 15 Vegetable Oil Unsaturated glycerides of C18:1Δ9,C18:2, Δ9 and 12 and C18:3 fatty acids Δ9, 12, 15 Tung Oil Unsaturatedglycerides of C18:1, C18:2, C18:3 fatty acids Meadowfoam Oil Unsaturatedglycerides of C20:1 fatty acids Δ5 Coriander Oil Unsaturated glyceridesof C15:1 fatty acids Δ6 Camelina Oil Unsaturated glycerides of C18:3fatty acids Δ9, 12, 15 Jatropha Oil Unsaturated glycerides of C18:,C18:2 fatty acids Crambe Oil or Unsaturated glycerides of C22:1 fattyacids Δ13 High Erucic Rapeseed Oil Algal Oil Polyunsaturated glyceridesof C22:6Δ4, 7, 10, 13, 16, 19 or of C20:5Δ5, 8, 11, 14, 17 fatty acids,plus saturated and unsaturated C14 to C18 fatty acids

Di- and polyunsaturated components of the starting composition producethe 1,4-cyclohexadiene during metathesis stage 100. Jatropha oils may beespecially appropriate, owing to large amounts of polyunsaturation andthe ability to grow in poor soils and poor conditions, where they do notcompete for acreage with edible vegetable oils. Algal oils are also mostuseful substrates of a starting composition according to thisdisclosure, since algal oils typically contain polyunsaturateddocosahexaenoic acid (C22:6) along with other acids. The relativeamounts of polyunsaturated acids in the starting oil can vary withgenetic factors as well as in response to growth conditions. The contentof the starting composition can thus be manipulated to some degree toprovide products having a desirable chain length and a desirable amountof cyclohexadiene via metathesis at block 100.

Algal oil metathesis processing presents a unique opportunity forpreparation of not only cyclohexadiene but also by-products useful forthe preparation of low melting fats, such as cocoa butter and shorteningand margarine comprising 0-trans fats. The algal oils comprise not onlytriglycerides (40%-80%) but also large amounts of galactolipids andphospholipids as well as phenolic antioxidants, hydrocarbons,terpenoids, and chlorophyll. Owing to the complex lipid mixtures foundin whole algae oil, it is advantageous, in applications, to producemethyl esters from the variety of galactolipids, phospholipids, andtriglycerides present. These fatty acid methyl esters (FAMEs) typicallycontain polyunsaturated fatty acid methyl esters (PUFA MEs) as well aslarge amounts of saturated esters, such as ME C14 and ME C16 whichcannot be easily separated, owing to the instability of the PUFA MEs andthe complexity of the lipid content. Cross-metathesis of FAME mixtureswith ethylene, according to an embodiment of this disclosure, providesconversion of FAMEs to short chain unsaturated FAMEs that can beseparated relatively easily (e.g., by distillation) along with thecyclohexadiene in the metathesis product. Production and utilization ofsuch metathesis products is discussed further hereinbelow.

Small olefins utilized in the metathesis reactions of block 100,including, without limitation, ethylene, propylene, butylene, andisobutylene, can be obtained relatively cheaply from a petroleumrefining process or can be obtained as by-products from catalyticvegetable oil cracking, without separation of the mixture. Inembodiments, the olefins utilized for metathesis at stage 100 comprisealpha olefins having from two to five carbon atoms.

In applications, the fuel and chemical production process disclosedherein provides tailored fuel and chemical products in an economicallydesirable manner. In applications, at least a portion of the end productis a high-value by-product. The disclosed process permits modificationand blending of fuelstocks to provide a blended fuel tailored to meetdesired fuel specifications.

Metathesis Catalyst. The metathesis reaction in metathesis stage 100 iscarried out in the presence of an amount of metathesis catalysteffective to catalyze metathesis reaction(s) to a desired extent. Themetathesis catalyst is any catalyst or catalyst system that catalyzesthe metathesis reaction. Any known metathesis catalyst may be employedalone or in combination with one or more additional catalyst. Suitablemetathesis catalysts include metal carbine catalysts based upontransition metals, including but not limited to ruthenium, chromium,rhenium, tungsten, molybdenum, and osmium. New catalysts conductmetathesis reactions of the unsaturated triglyceride oils with theolefins efficiently in the presence of the ester functional group.

Metathesis Methods. Specifications for a desired type of aviation fuelare satisfied by chemical compositions comprising alkanes (paraffins),isoalkanes (isoparaffins), cycloalkanes, and arylalkanes in specifiedproportions. To meet requirements for distillation range, viscosities,flash points, etc., the chain distributions for each fuel comprise arange of carbon chains appropriate for a fuel application, i.e., C9 toC14 for JP-8, as well as the distribution or blend of the various typesof components. Automotive fuels have similar requirements, but someproperties, such as cetane and flash point, can be extensively modifiedby additives. The key to achieving the appropriate blend and chaindistribution for an aviation spec fuel via this disclosure is to utilizeselected vegetable and algal oil precursors in an appropriate version ofthe metathesis reaction of the oil with selected olefin co-substrates atmetathesis block 100 and the further integration with appropriatedownstream conversion reactions at downstream processing block 200.Downstream processing stage 200 comprises production of both fuels atblock 400 and chemical intermediates or products at block 500.Downstream processing 200 generally further comprises separation ofmetathesis products at 300 prior to production of fuel at 400 andproduction of chemical product or intermediate at 500, as indicated inthe embodiment of FIG. 1. Substantially all of the carbons of thestarting composition are efficiently utilized to provide high-valueproducts, in certain applications of the disclosed method.

There are at least 12 ways to perform, at block 100, the metathesisreaction of an unsaturated fatty ester precursor. The preferred methoddepends on the type of lipid precursor available, desirablepre-processing, and the type of products desired. Methods of performingmetathesis at metathesis stage 100 include, without limitation:

(1) cross-metathesis on FAME with ethylene;(2) cross-metathesis on FAME with C2-C5 olefin mixture;(3) cross-metathesis on glyceride with ethylene;(4) cross-metathesis on glyceride with C2-C5 olefin mixture;(5) partial cross-metathesis on FAME with ethylene;(6) partial cross-metathesis on FAME with C2-C5 olefin mixture;(7) partial cross-metathesis on glyceride with ethylene;(8) partial cross-metathesis on glyceride with C2-C5 olefin mixture;(9) self-metathesis on FAME;(10) self-metathesis on glyceride;(11) partial self-metathesis on FAME; and(12) partial self-metathesis on glyceride.

The disclosed process integrates metathesis 100 comprising one or moreof these methods of performing metathesis reaction with downstreamprocessing 200 to provide one or more fuel and one or more chemicalproduct. For example, in embodiments, metathesis at 100 comprisescross-metathesis of algal oil within a starting composition with olefincomprising or consisting essentially of ethylene (Method 1 in the listhereinabove). The starting composition is converted into metathesisproduct comprising cyclohexadiene from the polyunsaturated portion ofthe oil; one or more alkene; and chain-shortened esters comprising atleast one carbon-carbon double bond. Downstream processing at 200comprises, producing a chemical intermediate or product at 500.Producing a chemical intermediate or product 500 may comprisehydrocarbonylating cyclohexadiene of the metathesis product to create adialdehyde. Producing a chemical intermediate or product at 500 mayfurther comprise subsequently converting the dialdehyde to abismethylamine, a dialcohol, or a dicarboxylic acid, all of which aresuitable intermediates for polymer synthesis. Downstream processing 200further comprises producing a fuel or fuel component from some of themetathesis products. Producing a fuel or fuel component 400 may comprisehydrotreating the chain-shortened esters and alkenes of the metathesisproduct over an isomerization catalyst to provide isoparaffin andparaffin components. The isoparaffin and paraffin components may be in aboiling range appropriate for jet fuels. Cyclohexadiene is also asuitable progenitor for the cycloparaffins and aromatics required formeeting the 25% alkylaromatic content of JP-8, and a portion of thecyclohexadiene of the metathesis product may be utilized at block 400 toproduce one or more fuel component. As discussed in more detailhereinbelow, the remaining saturated esters are utilizable as superbhigh-cetane methyl biodiesel additives at block 400, or are converted atblock 500 to low-melting triglycerides with a variety of uses in thefood, cosmetic, and/or personnel thermal protection products.

Processing Monounsaturated Oil. In embodiments, metathesis at block 100comprises cross-metathesis of oleate esters with alpha-olefins orethylene. FIG. 2 is a schematic of an integrated fuel and chemicalproduction process 20 comprising cross-metathesis of oleate esters ortriglycerides (I) with alpha-olefins or ethylene (II) and subsequentdownstream processing. In this process, R is alkyl or triglyceryl. Inembodiments, R is methyl. In embodiments, metathesis 101 reaction ofmonounsaturated (oleate) fatty esters I is carried out with an excess ofolefin II. In Case A, in which R′=alkyl (e.g., methyl, ethyl, propyl,etc.), product III comprises four types of new unsaturated metathesisproducts, IIIa, IIIb, IIIc, and IIId, as illustrated in FIG. 2. Whileonly cis-isomers are shown; trans-isomers will also be present. Using aC2 to C5 olefin mixture II, downstream processing 200 may comprisemildly hydrogenating the resulting C10 to C13 products with hydrogenover typical hydrogenation catalysts such as Pt and Pd to form mixturesof alkanes (C10 to C13) and fatty (C10 to C13) esters. In applications,downstream processing comprises production of fuel 401 bydecarboxylating the carboxylate groups to the alkane over a Pd catalyst.Downstream processing may further comprise isomerizing over anisomerization catalyst to generate isoparaffins in the same range.Desired mixtures of products for certain fuels are selectively producedby varying the composition of the olefin feed II in the metathesisreaction 101 with the oleate ester I. However, the complex productmixture produced via Case A is generally not viable for production ofchemicals other than azeleic acid, which may be produced via oxidation.Azelaic acid can more easily be provided directly from the startingfatty acid.

In applications, monounsaturated (oleate) fatty esters or triglyceride(I) are metathesized 101 with an excess of olefin II, where R′ ishydrogen, i.e., the olefin is ethylene. In this case, Case B, whereethylene is the olefin feedstock, only two metathesis products III areproduced (metathesis products IIIa and IIId). Downstream processing 200may comprise producing chemical feedstock 501 by converting theomega-unsaturated ester (IIIa) to a C11 aldehyde ester and subsequentlyto valuable amino and hydroxyl esters as described by Lysenko et al.(U.S. Patent Application No. 2005/0154221 A1) and Abraham et al. (PCTPatent Application PCT/US2007/021931). The reaction with ethylene, CaseB, provides, however, only 1-decene (IIId) as the alkene product, whichdoes not meet fuel specifications. It is thus difficult to make bothuseful chemicals and useful fuels using monounsaturated substrates andmethods.

Producing Chemicals and Fuels from Polyunsaturated Oils. For theproduction of both fuels and chemical or polymer intermediates or forproduction of multiple types or components of fuels, an alternativestrategy is employed which uses di- and polyunsaturated precursors, suchas those occurring in algal oils and many vegetable oils. Severalvegetable oils comprise triglycerides of polyunsaturated as well asmonounsaturated and saturated fatty acids. Suitable oils include,without limitation, oils from soybean, safflower, jatropha, sunflower,rapeseed, peanut, palm, cottonseed, and corn, which contain linoleate(18:2), and oils from linseed or flax, camelina, soybean, and palm,which contain linolenate (18:3). The precursors for the metathesisreaction can be simple alkyl esters produced in a preliminarytransesterification step or the natural triglyceride forms or a wholealgal oil comprising various forms of lipid ester. Consider the 12variations discussed above for conducting the metathesis reaction withthe di-unsaturated fatty ester, linoleate.

The metathesis products of metathesis stage 100 for these 12 methodsalong with fuel and chemical products produced in downstream processingstage 200 are presented in Table 2. The implications of using thevarious metathesis methods for production of fuels and chemicals viadownstream processing 200 are discussed in detail hereinbelow. FIG. 3 isa schematic of an integrated fuel and chemical production process 30,according to an embodiment of the invention, comprising cross-metathesisof vegetable oil or methyl ester and downstream processing. Exemplarilydepicted is cross-metathesis 102 of the linoleyl part of thetriglyceride oil or the linoleate methyl ester component IV andpotential downstream processing of the cross-metathesis products. Crossmetathesis 102 of the linoleyl part of the triglyceride oil or thelinoleate methyl ester component IV and olefin II produces metathesisproduct comprising cyclohexadiene V, olefins VI, and higher molecularweight triglycerides or esters IIIC. Importantly, the cyclohexadieneproduct (V) is easily separated from the higher-molecular-weightunsaturated triglycerides (IIIC) and olefins (VI) by separation 301.Separation 301 may comprise distillation, crystallization, or anothersuitable method of separating the metathesis products.

TABLE 2 Potential Intermediate and Final Products from Metathesis ofLinoleate (C18:2Δ9,12) Esters in Addition to the 1,4-Cyclohexadiene (CY)Metathesis Intermediate Products of Downstream Metathesis ProductsProcessing Method Ester Olefin Olefin(s) Ester(s) Chemical(s) Fuel(s) 1 - Cross FAME C2 C7:Δ1 ME¹ C10:Δ9 CY-der², C10 BD³ C8 + C11- der  2 -Cross FAME C2 to C7:Δ1 ME C10:Δ9 CY-der C10 to C13 C5 to C10:Δ4 to MEC13:Δ9 BD C9 to C13 jet C6 to C8 gasoline  3 - Cross Glyceryl C2 C7:Δ1GE⁴ C10:Δ9 CY-der, C10 BD C8 + C11- der  4 - Cross Glyceryl C2 to C7:Δ1GE C10:Δ9 CY-der C10 to C13 C5 to C10:Δ4 to GE C13:Δ9 BD C9 to C13 jetC6 to C8 gasoline  5 - Partial FAME C2 C7:Δ1 + ME C10:Δ9 + CY-der C10 +C13 BD Cross C10:2Δ1,4 ME C9 to C13 jet C13:2Δ9,12  6 - Partial FAME C2to C7:Δ1 + ME C10:Δ9 + CY-der C10 to C16 Cross C5 C10:2Δ1,4 ME BD toC10:Δ4 + C13:2Δ9,12 to C9 to C13 jet C13:Δ4,7 ME C13:Δ9 + ME C16:2Δ9,12 7 - Partial Glyceryl C2 C7:Δ1 + GE C10:Δ9 + CY-der C10 + C13 BD CrossC10:2Δ1,4 GE C13:2Δ9,12 C9 to C13 jet  8 - Partial Glyceryl C2 toC7:Δ1 + GE C10:Δ9 + CY-der C10 to C16 Cross C5 C10:2Δ1,4 GE BD toC10:Δ4 + C13:2Δ9,12 to C9 to C13 jet C13:Δ4,7 GE C13:Δ9 + GE C16:2Δ9,12 9 - Self FAME C12:Δ6 Me C15:Δ9 + CY-der C15 BD ME2 C18:Δ9 azeleic C9 toC15 jet 10 - Self Glyceryl C12:Δ6 GE C15:Δ9 + CY-der C15 BD GE2 C18:Δ9azeleic C9 to C14 jet 11 - Self FAME C12:Δ6 + Me C15:Δ9 + CY-der C15 BDPartial C15:2Δ6,9 ME2 C18:Δ9 + azeleic C9 to C14 jet ME2 C21:2Δ9,12 12 -Self Glyceryl C12:Δ6 + GE C15:Δ9 + CY-der C15 BD Partial C15:2Δ6,9 GE2C18:Δ9 + azeleic C9 to C12 jet GE2 C21:2Δ9,12 ¹ME = Methyl Ester(s) ²der= Derivative(s); ³BD = Biodiesel; ⁴GE = Glyceryl Ester(s)

Utilizing Method (1) hereinabove, cross metathesis 102 of ethylene(olefin II with R′ being hydrogen) with linoleate methyl ester (IV)gives 1,4-cyclohexadiene (V) plus 1-heptene (VI, R′═H) and methyl9-decenoate IIIc (R′═H) which are separable by fractional distillation.As pure methyl linoleate (or pure triglyceride) may be expensive toobtain, the metathesis products from vegetable oil may comprise amixture containing some 1-nonene (IIId) from metathesis of methyl oleateplus methyl stearate as well as the mentioned products from linoleate.Downstream processing 200 may comprise producing fuel blendstock 405 byhydroisomerizing the heptene to provide gasoline XXVII. However,hydrotreating these olefins and the decenoate to a jet or diesel fueldoes not provide the required distribution of longer-chain (C11-C14)components. Downstream processing 200 may comprise producing fuelblendstock 402 comprising the separated methyl decenoate IIIc (R′═H) orits hydrogenation product methyl decanoate, which are high-cetane methyldiesel additives VII. The cyclohexadiene distillation cut comprisingcyclohexadiene V is used to produce chemical feedstock 502. Thecyclohexadiene cut contains mono-olefin impurities, so it may be reactedvia hydrocyanation or hydrocarbonylation, to provide bis-adducts, suchas VIII, which are more easily separated by distillation from thecorresponding mono adducts from the mono-olefins and also the adductfrom the unsaturated ester. Thereby caprylonitrile and caprinitrile or,alternatively, capryl aldehyde and capraldehyde are produced from C7 andC9 olefin, respectively, in downstream reactions. Thus the ethylenecross-metathesis provides good access to chemical feedstocks and alsomethyl diesel VII if desired. Impure 1-heptene can also be reacted in asecond cross-metathesis with an olefin mixture to produce a range oflarger olefins (C9-C13) useful for converting to jet fuel byhydrogenation and isomerization. Use of glyceryl esters in Method 3(R=glyceryl) instead of methyl esters (R=methyl) is less desirable, astransesterification of IIIc (R′═H) is needed to obtain methyl biodieselVII.

When the cross-metathesis reaction 102 is performed with a C2-C5 olefinmixture II (Method 2), a mixture of new olefins VI (R′=alkyl, H) isobtained in addition to the cyclohexadiene V and C10 to C13 unsaturatedesters (IIIa, R′=alkyl, H). The new olefins VI comprise C7 to C10olefins from the alkyl end of the linoleate IV, as well as C4-C8 olefinsfrom reactions of the starting olefins II with themselves. Separation ofthe cyclohexadiene V from the resulting olefin mixture is far moredifficult by distillation in this case because of the variety of olefinspresent. However, the impure C6 distillation cut can be further reactedas described hereinbelow with respect to FIG. 5 to obtain purecyclohexane derivatives. In embodiments, the C2 to C5 cut is recycled.The C7-C8 cut can be isomerized at 405 to gasoline XXVII. At 404, 403,severe catalytic hydrogenation of the C9-C10 olefin cut and the C10 toC13 esters produces alkanes, isoalkanes, cycloalkanes XVI which can behydroisomerized/decarboxylated to jet fuel XXI. The C10 to C13 estersare also mildly hydrogenated at 402 to a methyl C10-C13 biodiesel VII.This method produces both chemical intermediates and jet or biodieselfuels with a good distribution of carbon chain lengths.

The use of glyceryl esters (Method 4) allows easier separation of theolefins from the esters in the metathesis products. This is not soimportant for linoleate but may be important in processing more highlyunsaturated oils. In embodiment, glyceryl esters from the metathesisproducts of a starting composition comprising glyceryl functional groupsR are transesterified to biodiesel VII or are used directly inconversion to jet fuel XXI.

Limiting the amount of olefin II or slowing the reaction results inpartial conversions of the polyunsaturated chains to produce dienes witha wider variety of chain lengths, at the expense of cyclohexadiene.Using Method 5 and especially Method 6 allows for formation of betterdistributions of components in both methyl biodiesel and jet fuelproducts. However, formation of C14 to C16 components from the C2 to C5olefin feed is not useful for jet fuel and is even high for diesel, butthe C14-C16 esters are useful for biodiesel. Thus the partial metathesisis used for highly polyunsaturated feeds rather than linoleate, becausethe distribution of chain lengths in the product olefins and esters willextend to the range required for jet fuel and diesel (see discussionhereinbelow).

Utilization of glyceryl esters with partial conversion (Methods 7 and 8)gives similar products, but separation of the esters from the olefins isfacilitated, owing to their very high molecular weights. This is usefulfor obtaining jet and biodiesel (after transesterification) in desirableranges.

The self-metathesis of methyl linoleate (Method 9) gives only the decenein addition to the cyclohexadiene and ester products. The 6-dodecene andthe C18 diester are of limited value, but the C15 ester is easilyobtained by distillation and used as biodiesel or hydrotreated to jet.Both unsaturated esters can be oxidized to azeleic acid.

Self-metathesis of the glyceryl linoleate (Method 10) likewise givesproducts of limited usefulness. Partial self-metathesis (Methods 11 and12) gives a wider variety of olefins and esters, but unfortunately, theproducts are larger and less useful for production of spec fuels.

Cyclohexadiene is formed in all of the metathesis reactions of linoleateesters. Less cyclohexadiene is formed from the partial reactions, sincethe central portion of the linoleate (C10-C12) is only partiallyconverted to cyclohexadiene and partially to diene intermediatescontaining the three extra carbons. Thus, in embodiments, to maximizeformation of chemical intermediates, the metathesis reaction at stage100 is run as far to completion as possible. In other embodiments,partial conversion by metathesis at stage 100 is utilized to maximizejet fuel production.

Thus to facilitate the production of fuels and chemicals via the methodof this disclosure, polyunsaturated esters IV are cross-metathesized 102with small olefins II as in the embodiment of FIG. 3. In embodiments,the separated olefin VI and unsaturated esters IIIc are hydrotreated toalkanes, isoalkane, and cycloalkanes XVI. Thus by using thepolyunsaturated precursors and an effective separation 301 between thecyclohexadiene V and the other metathesis products VI, IIIc, one canobtain both useful chemicals and fuels.

The metathesis product comprises cyclohexadiene V. Cyclohexadiene is thekey intermediate for downstream processing of metathesis products toproduce fuel blendstock components, chemical feedstocks, or bothaccording to the integrated method of this disclosure. In embodiments ofthe method, cyclohexadiene is used to produce valuable difunctionalmonomers for synthesis of polymers. In embodiments of the fuel andchemical production method, cyclohexadiene is utilized for synthesis ofcycloparaffins and/or aryl paraffins suitable for the production of JP-8fuel. FIG. 4 is a schematic of a downstream processing method 40,according to an embodiment of the invention, for synthesizingcycloparaffins and alkylaromatics via acid-catalyzed reaction ofcyclohexadiene with alpha-olefins. In the embodiment of FIG. 4,cycloparaffins and alkylaromatics are synthesized 407 via acid-catalyzedreaction of cyclohexadiene V with alpha-olefins II. In embodiments, R″is an alkyl group, selected from C₂-C₆ alkyl groups. Smalleralpha-olefin products (R″═C2 to C6), which may be obtained frommetathesis at 100, are reacted with cyclohexadiene V in the presence ofa strong acid catalyst to give alkylation products IX. The strong acidcatalyst may be H₂SO₄ or solid superacid catalyst. The alpha-olefin IIattaches at the second carbon of cyclohexadiene V to produce thebranched alkyl-substituted cyclohexadiene IX. This product IX isdisproportionated at 408 to a mixture of cycloparaffins X andalkylaromatics XI with chain lengths appropriate for jet fuel blends. Asdiscussed previously with regard to FIG. 3, the larger olefins (R″═C7 toC12) are hydrotreated at 406 to give alkanes and isoalkanes XVI suitablefor jet fuels XXI.

Producing chemical feedstock 500 may comprise synthesis of monomers.FIG. 5 is a schematic of a downstream processing method 50, according toan embodiment of the invention, for synthesizing disubstitutedcyclohexane intermediates suitable for synthesis of polymers. As shownschematically in FIG. 5, for the synthesis of monomers,1,4-cyclohexadiene V is converted at 503 to cyclohexane-dicarboxaldehydeXII by hydrocarbonylation with carbon monoxide and hydrogen. Inapplications, the cyclohexanedicarboxaldehyde XII is subsequentlyconverted at 504 to cyclohexanedimethanol XIII by hydrogenation, tocycloxanebismethylamine VIII by reductive amination at 505, and/or tocyclohexanedicarboxlic acid XV by oxidation at 506. Bifunctionalmonomers, XIII, VIII, and XV are suitable for the synthesis ofpolyesters, polyurethanes, polyamides, and/or polyureas. Inapplications, the 1,4-cyclohexadiene metathesis product V is convertedat 507 to the cyclohexanedinitrile XIV by hydrocyanation and,subsequently, to the bisamine VIII by hydrogenation of the nitrilegroups at step 508.

Linolenate triglyceride in oils also provides 1,4-cyclohexadiene V fromthe central portion (C10 to C15). Complete reaction of docosahexaeneoatefrom algal oil gives 2.5 moles of 1,4-cyclohexadiene from thepolyunsaturated chain, representing 15 of the 22 carbons. Anothercomponent of algal oil is eicosapentaenoate, which gives 2 moles ofcyclohexadiene, representing 12 of the 20 carbons.

Other variations of the disclosed method produce other specific fuelcomponents. In embodiments, aromatics are introduced as the R group byusing styrene or, perhaps, pyrolyzed waste polystyrene in thecross-metathesis. This provides C16 alkylbenzene, i.e., decylbenzene.Alternatively, the C10-C13 olefins are combined with benzene, toluene,or xylene using an acid catalyst to produce alkylaromatics, useful forsurfactant synthesis or for jet fuels.

Specialty fuels require a mixture of structural isomers of each of thechain lengths. These isomer mixtures are readily formed on anisomerization catalyst with minimal cracking if the feedstock is analkene. Thus, in embodiments, the alkene products (IIIb, IIId, VI, etc.)from the metathesis reactions in metathesis stage 100 described aboveare passed over an isomerization catalyst in downstream processing 200prior to hydrogenation to a final product.

Starting Composition Comprising Polyunsaturated Algal Oil

Substantially Complete Reaction of Polyunsaturated Chains. Aparticularly desirable embodiment of the fuel and chemical productionmethod of this disclosure is the integration of metathesis reactions atmetathesis stage 100 with downstream processing 200, wherein thestarting material comprising algal oil(s). FIG. 6 is a schematic of anintegrated fuel and chemical production process 60, according to anembodiment of the invention, comprising complete metathesis of algal oiland downstream processing, wherein complete metathesis comprisessubstantially complete reaction of the polyunsaturated chains of thealgal oil. Integrated processing scheme 60 comprises metathesis 103 ofalgal FAME XXII with complete reaction of the polyunsaturated chains ofthe algal FAME XXII with ethylene II′ (Method 1). The FAME XXII may beproduce via pretreatment of a starting composition comprisingpolyunsaturated algal oil with C14, C16, and C22:6Δ47, 10, 13, 16, 19lipids XXIII as discussed hereinabove. A typical algal FAME compositioncontains about equal amounts of ME C14, ME C16, and ME C22:6. When thecross-metathesis reaction 103 is taken to completion, as illustrated inFIG. 6, the products XXIV can easily be separated by simple distillation302, owing to the diverse boiling points thereof. Cross metathesis inthis manner produces large amounts of cyclohexadiene V and smalleramounts of 1-butene XXV. The 1-butene XXV is suitable as a coreactant inother metathesis reactions and/or in other chemical processing. Thecyclohexadiene V is converted to difunctional intermediates VIII, XIII,and/or XV for polymers as described hereinabove with respect to FIG. 5or to cycloparaffins X and/or XI as described hereinabove with respectto FIG. 4.

The ester components of the metathesis products XXIV comprise saturatedC14 to C18 FAME XXVI originally present in the starting composition plusthe unsaturated ester formed in the metathesis 103 of thepolyunsaturated FAME XXII. The unsaturated ester comprises 4-pentenoateXVII and/or 5-hexenoate from the C22:6 and/or C20:5 acyl groups,respectively.

Saturated FAMEs XXVI may be utilized at 409 for biodiesel VII. Inembodiments, the saturated FAMEs XXVI are obtained for reactions of theinteresterification type that yield valuable products.Interesterification 509 of the saturated ester product XXVI withtriolein (or canola oil) exchanges the C14-C18 saturated acids for twoof the oleyl groups in the triglyceride producing a low-meltingdisaturated acyl monooleylglyceride XVIII, similar to cocoa butter,margarine, and shortening. The reaction 509 is catalyzed by a lipaseenzyme, such as lipozyme RM IM from Rhizomucor miehei. The cisconfiguration of oleyl is conserved since no hydrogenation is performed,and metathesis 103 was conducted in an earlier step. Thus notrans-configurations are generated. The interesterification products areseparated by short path distillation, providing methyl oleate anddisaturated acyl monooleyl glyceride XVIII. These have melting points ofless than 100° F. These products are also valuable for the manufactureof protective gels that absorb large amounts of heat (because of meltingenthalpy) and can, therefore, keep body temperature in normal rangesduring exposure to excessive conditions. For example, a heat absorbingmaterial may be produced from the low-melting metathesis-modifiedtriglyceride. The heat absorbing material may be used to create a panelthat, when in contact with human skin, absorbs internal or externalheat, maintaining the skin at normal skin temperature.

Besides the important value of the cyclohexadiene V and saturated esterproduct XXVI as a chemical intermediate, the unsaturated ester products,e.g. XVII, and olefin products, e.g. XXV, are useful for production offuel and chemical products. Methyl 4-pentenoate XVII can be converted at510 to amino ester intermediates (e.g., VIII, XIII, and/or XV) viahydrocyanation and hydrogenation. The amino ester intermediates may thenbe polymerized to desirable polymers, for example, to nylon-6. Theolefin cross-metathesis products (e.g., XXV) obtained from the omega endof the fatty acids are valuable for providing several components of jetfuels. For example 1-butene XXV from the omega-3 fatty acids is reactedwith cyclohexadiene V in the alkylation reaction of FIG. 4 to providecycloparaffins X, XI. Alternatively or additionally, the 1-butene XXVcan be oligomerized to a series of alkenes (dimers, trimers, tetramers)from which isoparaffins for jet fuel XXI are produced.

Utilizing an olefin mixture with algal FAME (Method 2) results in largeamounts of cyclohexadiene V plus a mixture of short-chain unsaturatedesters and olefins. If the reactant olefins comprise C7:Δ1 to C10:Δ1 andalso C12:Δ6, then the resulting unsaturated esters comprise ME C10 toC13 and the product olefins C9 to C12, appropriate for hydrotreating tojet fuels. It should be recognized that the required C7 to C10 feed canbe obtained from the products of vegetable oil metathesis (Table 2).

Partial Reaction of Polyunsaturated Chains. Especially useful for theproduction of JP-8 fuels as well as bifunctional polymer intermediatesis a variation of the metathesis reaction of the algal FAME withethylene, wherein the metathesis reaction is only partially completed(Method 5). FIG. 7 is a schematic of an integrated fuel and chemicalproduction process 70, according to an embodiment of the invention,comprising partial metathesis 104 of algal and/or vegetable fatty acidmethyl ester(s) or “FAME,” and downstream processing of metathesisproducts; partial metathesis comprises limited (partial) reaction of thepolyunsaturated chains of the algal FAME and/or vegetable FAME toprovide distributions of chain lengths in the resulting products.Starting composition comprising algal FAME XXII is partialcross-metathesized at 104 with ethylene II′ to produce metathesisproducts comprising cyclohexadiene V, unsaturated ester products XIX,saturated ester components XXVI, and olefin products XX.

The metathesis reaction 104 can be controlled by using low temperatures,short reaction times, small amounts of catalyst, and/or a small amountof olefin coreactant II′. In this embodiment, partial cross metathesisat step 104 of the polyunsaturated chain of FAME XXII with ethylene II′provides a mixture of products, where one or more of the double bondshas reacted. Thus the product still contains some cyclohexadiene V forchemical synthesis, but the olefin portion XX and unsaturated esterportions XIX now contain a distribution of chain lengths andmulti-unsaturation, as indicated in FIG. 7. This is a result of cleavageat various points (double bonds) in the C22 chain. Distillation 303 orother suitable separation method is used to separate cyclohexadiene V,olefin portion XX, and unsaturated ester portion XIX. Hydrogenation andisomerization of this product mixture provides a better distribution ofchain lengths in the product fuel(s). The C4-C8 components of theunsaturated olefin and unsaturated ester portions XX and XIXrespectively may be hydrogenated and isomerized at 410 to gasolineXXVII. The C9-C14 components of the unsaturated ester and olefinportions XIX and XX respectively may be hydrogenated and isomerized at411 to provide jet fuel XXI. The C14-C17 esters, including saturatedC16, 14 esters, may be utilized at 412 for biodiesel VII. Thecyclohexadiene V is converted at 511 to difunctional intermediates VIII,XIII, and/or XV for polymer synthesis as described hereinabove withrespect to FIG. 5 and/or to cycloparaffins X and/or XI at 413 asdescribed hereinabove with respect to FIG. 4.

Examples

Partial cross-metathesis of safflower oil with ethylene (1:10 molarratio) was conducted in a stirred autoclave at 25° C. with acommercially available metathesis catalyst (Grubbs second-generationcatalyst). Safflower oil contains mostly oleic (18:1) and linoleic acid(18:2) and small amounts of saturated acids. Olefin products wereseparated from the shortened-chain glyceryl esters by distillation.These olefin products included 1,4-cyclohexadiene, 1-heptene, 1-decene,6-dodecene, and 6-pentadecene and small amounts of 1,4-decadiene,1,4-tridecadiene, 9-octadecene, 6,9-octadecadiene, and 9,12-uncosadieneand very small amounts of other hydrocarbons. Several of the productsindicate incomplete reaction with the ethylene, which is beneficial forfuel production.

The olefins are distilled such that a “kerosene range” cut (C10 to C15)is obtained, which is then hydrotreated with a catalyst that partiallyisomerizes and hydrogenates the olefins to produce a mixture ofparaffins and isoparaffins (C10 to C15). Such catalyst comprises a GroupVIII metal (Pd, Pt, Ni) on a zeolitic or acidic support (H-beta, ZSM22,ZSM23, SAPO-11). The high selectivity of this process results in highconversion to a C10 to C15 product with a boiling range appropriate forjet fuel (205°-300° C.).

Cyclohexadiene is recovered from the distillation and converted eitherto alkyl cyclohexanes (cycloparaffins) for addition to the jet fuels oris hydrocarbonylated and hydrocyanylated to form polymer precursors. Thehigher distillation cut is cycled to subsequent oil metathesisreactions.

The separated glyceryl ester portion of the product from safflower oilincludes some oligomeric material resulting from reversion orself-metathesis. The glyceryl residue is treated with methanol and abasic catalyst to form the methyl esters of the altered chain fattyacids. This product comprises methyl esters of 9-decenoic acid (mainly),9,12-tridecenoic acid, 9-pentadecenoic acid, and 9-octadecendioic acidand contains a small amount of unreacted oleic, linoleic, and saturatedacids. This product is hydrotreated with a Pd catalyst on a zeoliticsupport to produce C9 to C18 paraffins and isoparaffins. Processing ofthe acid portion of the triglyceride product to jet fuel blendstock canalso be accomplished by hydrotreating the fatty acid mixture obtained bybasic hydrolysis or even by hydrotreating directly the shortened-chaintriglycerides.

The self-metathesis reaction of flax oil with the Grubbssecond-generation catalyst at 40° C. gives a different set of products.The glyceryl esters form a cross-linked gel. The olefins separated bydecantation from the gel comprise the following set: 3-hexene,1,4-cyclohexadiene, 6-dodecene, 6-pentadecene, and 9-octadecene. Onlyvery small amounts of partially reacted chains were present from thereaction at this temperature. The glyceryl esters were essentially9-decenoic and 9-octadecenoic esters.

Additional reactions include Diels-Alder addition (2+4 cycloaddition) ofbutadiene or cyclopentadiene to the alkenes and cyclohexadiene to formC14 to C17 alkylcyclohexenes and bicyclic alkenes for synthesis ofhigh-energy fuels, similar to RJ-4, RJ-5, and JP-10.

While preferred embodiments of the invention have been shown anddescribed, modifications thereof can be made by one skilled in the artwithout departing from the spirit and teachings of the disclosure. Theembodiments described herein are exemplary only and are not intended tobe limiting. Many variations and modifications of the inventiondisclosed herein are possible and are within the scope of the invention.Where numerical ranges or limitations are expressly stated, such expressranges or limitations should be understood to include iterative rangesor limitations of like magnitude falling within the expressly statedranges or limitations (e.g., from about 1 to about 10 includes, 2, 3, 4,etc.; greater than 0.10 includes 0.11, 0.12, 0.13, etc.). Use of theterm “optionally” with respect to any element of a claim is intended tomean that the subject element is required, or alternatively, is notrequired. Both alternatives are intended to be within the scope of theclaim. Use of broader terms such as comprises, includes, having, etc.,should be understood to provide support for narrower terms such asconsisting of, consisting essentially of, comprised substantially of,etc.

Accordingly, the scope of protection is not limited by the descriptionset out above but is only limited by the claims which follow, that scopeincluding all equivalents of the subject matter of the claims. Each andevery claim is incorporated into the specification as an embodiment ofthe present invention. Thus the claims are a further description and arean addition to the preferred embodiments of the present invention. Thediscussion of a reference is not an admission that it is prior art tothe present invention, especially any reference that may have apublication date after the priority date of this application. Thedisclosures of all patents, patent applications, and publications citedherein are hereby incorporated by reference, to the extent they provideexemplary, procedural, or other details supplementary to those set forthherein.

1. A method comprising: providing a starting composition comprising apolyunsaturated fatty acid, a polyunsaturated fatty ester, a carboxylatesalt of a polyunsaturated fatty acid, a polyunsaturated triglyceride, ora mixture thereof; self-metathesizing the starting composition orcross-metathesizing the starting composition with at least oneshort-chain olefin in the presence of a metathesis catalyst to formmetathesis products comprising: cyclohexadiene; one or more olefincompounds; and one or more acid-, ester-, or salt-functionalized alkenecomprising at least one carbon-carbon double bond; and reacting at leasta portion of the cyclohexadiene to produce at least one selected fromthe group consisting of cycloalkanes and cycloalkane derivatives.
 2. Themethod of claim 1 further comprising utilizing the cycloalkanes for fuelblendstock.
 3. The method of claim 1 wherein reacting the at least aportion of the cyclohexadiene comprises catalytically reacting at leasta portion of the cyclohexadiene to produce disubstituted ordi-functionalized cyclohexane derivatives.
 4. The method of claim 3wherein the disubstituted or di-functionalized cyclohexane derivativeshave the formula C₆H₁₀X₂, where X is selected from the group consistingof CN, CHO, and CH₂NH₂.
 5. The method of claim 4 wherein thedisubstituted or di-functionalized cyclohexane derivatives arecyclohexanedicarboxaldehyde derivatives having the formula C₆H₁₀(CHO)₂.6. The method of claim 5 further comprising reducing the carboxaldehydegroups to form alcohol groups.
 7. The method of claim 4 wherein thedisubstituted or di-functionalized cyclohexane derivatives are dinitrilederivatives having the formula C₆H₁₀(CN)₂.
 8. The method of claim 7further comprising hydrolyzing the nitrile groups to form carboxylicacid groups.
 9. The method of claim 7 further comprising hydrogenatingthe nitrile groups to form amine groups.
 10. The method of claim 1wherein the cycloalkane derivatives comprise alkylcyclohexanederivatives having the formula C₆H₁₁R, where R is selected from alkylgroups.
 11. The method of claim 10 wherein reacting the at least aportion of the cyclohexadiene comprises reacting cyclohexadiene with afeed comprising olefins.
 12. The method of claim 11 wherein at least aportion of the olefins in the feed comprising olefins were produced viathe metathesis reaction.
 13. The method of claim 1 further comprisingconverting at least one of the metathesis products to produce at leastone fuel blendstock component selected from alkanes, isoalkanes, andcycloalkanes.
 14. The method of claim 13 wherein the at least one fuelblendstock has a chain length in the range of from eight to fourteencarbon atoms.
 15. The method of claim 14 where the fuel blendstock issuitable for use in at least one selected from the group consisting ofJP-4, JP-5, JP-8, Jet A, and Jet A1 fuels.
 16. The method of claim 15further comprising tailoring the fuel blendstock by limiting themetathesis reaction by adjusting at least one selected from the reactiontemperature, reaction time, amount of catalyst, and amount ofco-reactant olefin, whereby a desired comprehensive distribution ofchain lengths is obtained from partial completion of the metathesisreaction.
 17. The method of claim 1 further comprising converting atleast a portion of the metathesis products to azeleic acid.
 18. Themethod of claim 1 wherein the starting composition comprises vegetableoil.
 19. The method of claim 1 wherein the starting compositioncomprises algal oil.
 20. The method of claim 1 wherein the one or moreolefin metathesis product comprises light olefins selected from1-propene and 1-butene, and wherein the method further comprisesoligomerizing the light olefin product to produce kerosene fuelcomponents having chain lengths in the range of from about eight tosixteen carbons.
 21. The method of claim 20 wherein oligomerizingcomprises treatment with strong acid.
 22. The method of claim 1comprising cross-metathesis of a starting composition comprising algaloil, and wherein the at least one short chain olefin comprises ethylene.23. The method of claim 22 wherein the at least one short chain olefinconsists essentially of ethylene.
 24. The method of claim 1 comprisingcross-metathesis of a starting composition comprising omega-unsaturatedvegetable oil containing linolenic acid.
 25. The method of claim 24wherein the vegetable oil is selected from the group consisting offlaxseed, rapeseed, camelina, soy, and palm oils.
 26. The method ofclaim 1 wherein the starting composition comprises algal oil, andwherein the metathesis product comprises one or more olefin compounddetermined by the selection of the at least one short chain olefinco-reactant, an unsaturated carboxylic acid or ester with five or morecarbons and unsaturation at C-4, and a saturated ester fraction.
 27. Themethod of claim 26 further comprising processing the saturated esterfraction via selective lipase reaction.
 28. The method of claim 27wherein selective lipase reaction comprises lipase-catalyzedinteresterification of an acyl portion of the saturated ester fractionwith canola oil, and wherein interesterification produces a low-meltingpoint modified triglyceride comprising saturated and monounsaturatedfatty acids and having a melting point in the range of from about 90° F.to about 100° F.
 29. The method of claim 28 further comprising producinga heat-absorbing material from the low-melting point modifiedtriglyceride.
 30. The method of claim 29 wherein the heat-absorbingmaterial comprises a panel that is capable of absorbing external orinternal heat, when in close contact with human skin, maintaining theskin at normal skin temperature.
 31. A method of producing at least onefuel or fuel component and at least one chemical product from a startingcomposition comprising a polyunsaturated fatty acid, a polyunsaturatedfatty ester, a carboxylate salt of a polyunsaturated fatty acid, apolyunsaturated triglyceride, or a mixture thereof, the methodcomprising: self-metathesizing the starting composition orcross-metathesizing the starting composition with at least oneshort-chain olefin in the presence of a metathesis catalyst to formmetathesis products comprising: cyclohexadiene; one or more olefincompounds; and one or more acid-, ester-, or salt-functionalized alkenecomprising at least one carbon-carbon double bond; utilizing a firstportion of the metathesis products to produce a fuel blendstock; andutilizing a second portion of the metathesis products to produce achemical product.
 32. The method of claim 31 wherein the chemicalproduct is selected from difunctional cyclohexane derivatives anddisaturated acyl mono-oleyl glycerides having melting points of lessthan 100° F.